Sven Jachalke

How to measure the pyroelectric coefficient

The precise quantification of the pyroelectric coefficient p is indispensable for the characterization of pyroelectric materials and the development of pyroelectric-based devices, such as radiation sensors or energy harvesters. A summary of the variety of techniques to measure p is given in the present review. It provides a classification after the thermal excitation and an outline of capabilities and drawbacks of the individual techniques. The main selection criteria are: the possibility to separate different contributions to the pyroelectric coefficient, to exclude thermally stimulated currents, the capability to measure p locally, and the requirement for metallic electrodes. This overview should enable the reader to choose the technique best suited for specific samples.

Dielectric to pyroelectric phase transition induced by defect migration

Subjecting strontium titanate single crystals to an electric field in the order of 106 V m−1 is accompanied by a distortion of the cubic crystal structure, so that inversion symmetry vanishes and a polar phase is established. Since the polar nature of the migration-induced field-stabilized polar (MFP) phase is still unclear, the present work investigates and confirms the pyroelectric structure. We present measurements of thermally stimulated and pyroelectric currents that reveal a pyroelectric coefficient pMFP in the order of 30 μC K−1m−2. Therefore, a dielectric to pyroelectric phase transition in an originally centrosymmetric crystal structure with an inherent dipole moment is found, which is induced by defect migration. From symmetry considerations, we derive space group for the MFP phase of SrTiO3. The entire electroformation cycle yields additional information about the directed movement and defect chemistry of oxygen vacancies.

The pyroelectric coefficient of free standing GaN grown by HVPE

The present study reports on the temperature dependent pyroelectric coefficient of free-standing and strain-free gallium nitride (GaN) grown by hydride vapor phase epitaxy (HVPE). The Sharp-Garn method is applied to extract the pyroelectric coefficient from the electrical current response of the crystals subjected to a sinusoidal temperature excitation in a range of 0 °C to 160 °C. To avoid compensation of the pyroelectric response by an internal conductivity, insulating GaN crystals were used by applying C, Mn, and Fe doping during HVPE growth. The different pyroelectric coefficients observed at room temperature due to the doping correlate well with the change of the lattice parameter c. The obtained data are compared to previously published theoretical and experimental values of thin film GaN and discussed in terms of a strained lattice.

Pyroelectricity of silicon-doped hafnium oxide thin films

Ferroelectricity in hafnium oxide thin films is known to be induced by various doping elements and in solid-solution with zirconia. While a wealth of studies is focused on their basic ferroelectric properties and memory applications, thorough studies of the related pyroelectric properties and their application potential are only rarely found. This work investigates the impact of Si doping on the phase composition and ferro- as well as pyroelectric properties of thin film capacitors. Dynamic hysteresis measurements and the field-free Sharp-Garn method were used to correlate the reported orthorhombic phase fractions with the remanent polarization and pyroelectric coefficient. Maximum values of 8.21 µC cm−2 and −46.2 µC K−1 m−2 for remanent polarization and pyroelectric coefficient were found for a Si content of 2.0 at%, respectively. Moreover, temperature-dependent measurements reveal nearly constant values for the pyroelectric coefficient and remanent polarization over the temperature range of 0 ° C to 1...

Anomalous ferroelectricity in P(VDF70-TrFE30)

ABSTRACT The ferroelectric phase transition of copolymers of vinylidene fluoride (VDF) with trifluoroethylene (TrFE) is well known and related to conformational changes in the polymer chain. Contrary to the expected paraelectric behaviour in the high temperature phase a pyroelectric investigation of the phase transition in the range from 0°C to 130°C combined with X-ray diffraction indicate the copolymer as ferroelectric when prepared and polarised in the high-temperature phase. Based on this finding the orthorhombic space-group Fmm2 is proposed for the polar high-temperature phase. Above the Curie temperature the material exhibits pyroelectricity with inverted sign, whose origin is interpreted as flexoelectricity.

Functionality from real structure: the oxygen vacancy in strontium titanate

According to Bhalla et al. the ABX3 perovskite system is the single most versatile structure family regarding material properties. The wide range of functionalities is realised through manifold combinations of constituents for the Aand B-site in the structure. In confirmation and extension of this abundance of properties also the real structure has a profound influence on the properties of the material. Here, we discuss the oxygen vacancy VO as the dominating point defect in the aristotype perovskite strontium titanate SrTiO3 and demonstrate how functionality can be realised by reversible redistribution processes within an external electric field. Specifically, the anisotropic migration behaviour of oxygen vacancies [1] along the different orientations of the crystal and how their redistribution results in a polar modification of the surface region of strontium titanate migration-induced field-stabilised polar phase or MFP phase [2] will be treated. The MFP phase is created by the application of a static electric field of approximately 1MV/m, in which charged defects like oxygen vacancies redistribute. In the migration process cubic unit cells are distorted into tetragonal ones and stabilised by the field. The polar structure of the modified perovskite entails new properties like pyroand piezoelectricity [3,4]. Furthermore, the process of creating the MFP phase in strontium titanate reversibly deposits energy in the crystal, thus making it a complete solid state battery.

Defect separation in strontium titanate: Formation of a polar phase

Stoichiometric perovskite-type strontium titanate acts as an insulator because of its wide electronic band gap and has therefore great potential as high-k dielectric and storage material in memory applications. Degradation phenomena of insulating properties of transition metal oxides occur during long time voltage application. From the defect chemistry point of view the question arises how mobile species react on an external electric field and which impact the redistribution has on the stability of the crystal structure. Here, we discuss near-surface reversible structural changes in SrTiO3 single crystals caused by oxygen vacancy redistribution in an external electric field. We present in-situ X-ray diffraction during and after electroformation. Several reflections are monitored and show a tetragonal elongation of the cubic unit cell. Raman investigations were carried out to verify that the expansion involves a transition from the centrosymmetric to a less symmetric structure. Regarding a whole formation cycle, two different time scales occur: a slow one during the increase of the lattice constant and a fast one after switching off the electric field. Based on the experimental data we suggest a model containing the formation of a polar SrTiO3 unit cell stabilized by the electric field, which is referred to as migrationinduced field-stabilized polar phase [1] at room temperature. As expected by a non-centrosymmetric crystal structure, pyroelectric properties will be presented in conjunction with temperature modulated electroformation cycles. Furthermore, we show that intrinsic defect separation establishes a non-equilibrium accompanied by an electromotive force. A comprehensive thermodynamic deduction in terms of theoretical energy and entropy calculations indicates an exergonic electrochemical reaction after the electric field is switched off. Based on that driving force the experimental and theoretical proof of concept of a solid-state SrTiO3 battery is reported.

Evaluation of structural phase transition by pyroelectric measurements

In non-centrosymmetric crystalline matter, marked by the pyroelectric effect, a change in temperature alters the materials spontaneous polarization, which further changes the charge density on the materials surface. This results in a current flow trough an external circuit, which differs drastically at the boundary between two crystallographic phases. Therefore, pyroelectric materials offer a great potential of low-temperature waste heat recovery by utilizing e.g. the Olsen-Cylce to convert residual heat into electric energy. A previous characterization is necessary to determine the operating conditions of the active material. This work presents a method to evaluate temperature depended pyroelectric properties, especially the pyroelectric coefficient p and the phase transition temperture TC, with the help of a computer controlled thermal/electrical stimulation and a simultaneously recording of the electrical response of the material. Here, the analysis with the Sharp-Garn-method [1] separates the pyroelectric from eventually disturbing non-pyroelectric signal, enabling the characterization of p and TC over a broad spectrum of materials, ranging from inorganic single crystals and ceramics to organic polymers.